WO2011131610A1 - Wärmeträger-medium auf schwefel-basis und verwendung des wärmeträger-mediums - Google Patents
Wärmeträger-medium auf schwefel-basis und verwendung des wärmeträger-mediums Download PDFInfo
- Publication number
- WO2011131610A1 WO2011131610A1 PCT/EP2011/056111 EP2011056111W WO2011131610A1 WO 2011131610 A1 WO2011131610 A1 WO 2011131610A1 EP 2011056111 W EP2011056111 W EP 2011056111W WO 2011131610 A1 WO2011131610 A1 WO 2011131610A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- heat transfer
- transfer medium
- halogenated hydrocarbon
- medium according
- additive
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Ceased
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/08—Materials not undergoing a change of physical state when used
- C09K5/10—Liquid materials
- C09K5/12—Molten materials, i.e. materials solid at room temperature, e.g. metals or salts
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F24—HEATING; RANGES; VENTILATING
- F24S—SOLAR HEAT COLLECTORS; SOLAR HEAT SYSTEMS
- F24S80/00—Details, accessories or component parts of solar heat collectors not provided for in groups F24S10/00-F24S70/00
- F24S80/20—Working fluids specially adapted for solar heat collectors
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/40—Solar thermal energy, e.g. solar towers
- Y02E10/46—Conversion of thermal power into mechanical power, e.g. Rankine, Stirling or solar thermal engines
Definitions
- the invention relates to a heat-transfer-medium comprising a mixture of elemental sulfur and at least one To ⁇ set.
- a use of the heat transfer medium is specified.
- Solar thermal power plants are based on the conversion of solar energy into electrical energy.
- parabolic trough power plants in a solar collector field by means of numerous, cascaded and parabolic shaped mirror incident sun rays focused on a so-called Receiver tube directed to a circulating ⁇ located therein heating heat transfer fluid (heat transfer medium, "HTF”) to heat.
- HTF heat transfer medium
- the thermal energy introduced in this way is converted into steam or hot gas via a heat exchange process and emitted into electrical energy by means of a turbine (power block).
- Elemental sulfur is basically suitable as a heat transfer medium for such an application. Sulfur melts at about 119 ° C and boils at 440 ° C (under normal pressure). Furthermore, liquid sulfur has a relatively high heat capacity c p of about 1.12 J / (gK) and a relatively high thermal conductivity ⁇ of about 0.17 W / (mK).
- the object of the invention is to develop a heat transfer medium based on elemental sulfur such that it can be used as a heat transfer fluid.
- a heat transfer medium comprising a mixture with elemental sulfur and at least ei ⁇ nem additive specified.
- the heat transfer medium is characterized in that the additive has at least one halogenated hydrocarbon.
- a use of the heat transfer medium of the heat transfer medium for re ⁇ versible energy storage is specified.
- the heat carrier medium absorbs energy and releases the absorbed energy.
- the idea underlying the invention is to modify the sulfur with the aid of halogenated hydrocarbons.
- hydrocarbons all types come hydrocarbon molecules in question, which is saturated, unsaturated (for example aromatic), cyclic, acyclic, branched and straight- ⁇ chain hydrocarbon molecules.
- the hydrocarbon may comprise only one kind of hydrocarbon molecules.
- mixtures of different hydrocarbon molecules all kinds of used Kohlenwas ⁇ serstoff molecules may be halogenated.
- a mixture of halogenated and non-halogenated hydrocarbon molecules can also be used.
- At least one kind of hydrocarbon molecules on halogenated ⁇ ned At least one hydrogen of the halogenated hydrocarbon is replaced by a halogen atom, ie fluorine, chlorine, bromine or iodine. Preferably, chlorine and bromine are used.
- a single hydrogen atom of the halogenated hydrocarbon may be replaced by a halogen atom.
- the halogenated hydrocarbon is a polyhalogenated hydrocarbon.
- the water ⁇ atoms of the halogenated hydrocarbon may be replaced by a type of halogen atom or through different types of halogen atoms.
- a halo gen- ⁇ Contribution to molecular weight of a single hydrocarbon material ⁇ molecule is relatively high.
- a halo gen- ⁇ Contribution to molecular weight of the halogenated hydrocarbons substance from the range of 25 wt .-% to 75 wt% selected out.
- a higher proportion, for example up to 90 wt .-% or a lower proportion, for example up to 10 wt .-% is also conceivable.
- a carbon skeleton of the halogenated hydrocarbon or halogenated hydrocarbons may have any number of carbon atoms.
- the carbon skeleton of the halogenated Kohlenwas ⁇ serstoffs have any carbon chain length.
- an average carbon chain length of the halogenated hydrocarbon is C 2 to C 30.
- the coals ⁇ carbon chain of the halogenated hydrocarbon is derived from two carbon atoms up to 30 carbon atoms. More than 30 carbon atoms per carbon chain are just ⁇ conceivable.
- a halogenated methane derivative having only a single, the backbone of the ha ⁇ logen faced lying carbon atom can be used.
- the halogenated hydrocarbon is preferably long-chain having a carbon chain length of above C 10.
- the halogenated hydrocarbon is a paraffin.
- the paraffin skeleton can do this unbranched (n-paraffin) or branched (iso-paraffin).
- the paraffin may be short chain, medium long chain or long chain.
- the paraffin is, for example, a short chain chlorinated paraffin (SCCP, Cio - C13), a medium chain chlorinated paraffin (MCCP, C14 - C17) or a long chain
- Chlorinated paraffin (LCCP,> Cis) ⁇ mixtures of said paraffins are also conceivable.
- any non-halogenated hydrocarbons which may be present with respect to the skeleton of the halogenated hydrocarbon.
- This ⁇ be indicated, for example, that in addition to halogenated Pa ⁇ raffinen non-halogenated paraffins can also be used.
- a proportion of the additive in the mixture can be individually adapted in depen ⁇ pending on the nature of the additive or the types of additives. It has proven to be particularly advantageous if the additive is present in a proportion of the mixture selected from the range from 0.01% by weight to 15% by weight. Higher levels of up to 20 wt .-% or up to 30 wt .-% are also possible.
- the mixture has at least one further additive selected from the group consisting of organic polysulfide, fatty acid, metal salt of a fatty acid, castor oil and nano-particles.
- the nanoparticles have an average particle diameter of 1 nm up to 100 nm.
- the nanoparticles Kings be ⁇ nen organic or inorganic. Mixtures of organic and inorganic nanoparticles are also conceivable.
- metals, semimetals, oxides and nitrides and sulfides or polysulfides of metals and / or Semi-metals and mixtures of the compounds mentioned are used.
- the castor oil is based on hydrogenated and / or dehydrogenated castor oil (hydrated, dehydrated Castor Oil) or as on Deriva ⁇ th.
- the organic polysulfide may have saturated and unsaturated hydrocarbon fragments.
- Ri and R2 are alkyl radicals of the carbon chain length of C2 to C 8 and especially the carbon chain length C9 to C are 1 2.
- R 1 and R 2 may also each be a methyl radical or a methyl radical derivative.
- the further addition of a fatty acid and / or a metal salt of fatty acid where the fatty acid at ⁇ having a carbon chain length from Be ⁇ rich from C2 to C2 0th
- a fatty acid and / or a metal salt of fatty acid where the fatty acid at ⁇ having a carbon chain length from Be ⁇ rich from C2 to C2 0th
- the halogen content of the organic, halogenated carbon-hydrogen derivative is advantageously 25 wt .-% - 75 wt.
- Ci to C30 The average carbon chain length of at any rate ver ⁇ -inverting organic, halogenated hydrocarbon derivative is Ci to C30 is (so-called chlorinated and / or brominated aliphatic compounds, paraffins and waxes).
- the content of the organic, halogenated hydrocarbon derivative to be used in each case is between 0.01-15% by weight of the total mass of the mixture used as the heat transfer medium.
- the proportion of any additional additives be ⁇ contributes a total of 0.01-15 wt .-% of the total mass of the mixture used as a heat transfer medium.
- HTF heat transfer fluid
- the heat transfer medium is used as a heat reservoir (storage medium) for the purpose of reversible energy storage (so-called latent heat storage, thermal energy storage, TES).
- TES thermal energy storage
- the property profile of the heat transfer medium also allows use as a storage medium, since in this way no separation of the separate liquid circuit ⁇ runs must be completed.
- the critical component of this overall process is namely in a special way the heat ⁇ carrier medium is that used to transport the solar thermal energy to heat exchanger or storage medium, as special physical, tech ⁇ niche and market requirements are placed on such a heat transfer medium.
- the subject of the embodiments is in each case a varnishträ ⁇ ger medium based on sulfur.
- the heat transfer medium is in each case a mixture with elemental sulfur as the main component.
- An additive in the form of a halogenated hydrocarbon is included in the mixture.
- the heat transfer medium has, in addition to sulfur, an additive in the form of MCCP (polychlorinated paraffin).
- MCCP polychlorinated paraffin
- the halogen content in the MCCP is about 70 wt .-% of the molecular weight.
- LCCP with a halogen content of about 70% by weight is also used.
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Thermal Sciences (AREA)
- Physics & Mathematics (AREA)
- Combustion & Propulsion (AREA)
- Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Mechanical Engineering (AREA)
- General Engineering & Computer Science (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Engine Equipment That Uses Special Cycles (AREA)
- Paper (AREA)
Abstract
Description
Claims
Priority Applications (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US13/641,951 US20130037741A1 (en) | 2010-04-20 | 2011-04-18 | Heat transfer medium based on sulphur and use of the heat transfer medium |
| EP11717526A EP2536807A1 (de) | 2010-04-20 | 2011-04-18 | Wärmeträger-medium auf schwefel-basis und verwendung des wärmeträger-mediums |
| AU2011244423A AU2011244423A1 (en) | 2010-04-20 | 2011-04-18 | Heat transfer medium based on sulphur and use of the heat transfer medium |
| CN201180019725XA CN102834482A (zh) | 2010-04-20 | 2011-04-18 | 基于硫的载热介质和该载热介质的用途 |
| BR112012027049A BR112012027049A2 (pt) | 2010-04-20 | 2011-04-18 | meio de transferência de calor à base de enxofre e uso do meio de transferência de calor |
| IL222471A IL222471A0 (en) | 2010-04-20 | 2012-10-16 | Heat transfer medium based on sulphur and use of the heat transfer medium |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE102010015632.9 | 2010-04-20 | ||
| DE102010015632A DE102010015632A1 (de) | 2010-04-20 | 2010-04-20 | Wärmeträger-Medium auf Schwefel-Basis und Verwendung des Wärmeträger-Mediums |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2011131610A1 true WO2011131610A1 (de) | 2011-10-27 |
Family
ID=44276254
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/EP2011/056111 Ceased WO2011131610A1 (de) | 2010-04-20 | 2011-04-18 | Wärmeträger-medium auf schwefel-basis und verwendung des wärmeträger-mediums |
Country Status (9)
| Country | Link |
|---|---|
| US (1) | US20130037741A1 (de) |
| EP (1) | EP2536807A1 (de) |
| CN (1) | CN102834482A (de) |
| AU (1) | AU2011244423A1 (de) |
| BR (1) | BR112012027049A2 (de) |
| CL (1) | CL2012002939A1 (de) |
| DE (1) | DE102010015632A1 (de) |
| IL (1) | IL222471A0 (de) |
| WO (1) | WO2011131610A1 (de) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013178930A1 (fr) | 2012-06-01 | 2013-12-05 | Arkema France | Soufre liquide de faible viscosité |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3508552A1 (de) | 2018-01-05 | 2019-07-10 | Castrol Limited | Phasenwechselmaterial für wärmeaustauschfluid/kühlmittel |
| GB201811002D0 (en) * | 2018-07-04 | 2018-08-15 | Bp Plc | Dielectric thermal management fluids and methods for using them |
| GB201811003D0 (en) | 2018-07-04 | 2018-08-15 | Bp Plc | Multiple cooling circuit systems and methods for using them |
| GB201905733D0 (en) | 2019-04-24 | 2019-06-05 | Bp Plc | Dielectric thermal managment fluids and methods for using them |
| CN119242273B (zh) * | 2024-09-27 | 2025-12-09 | 华中科技大学 | 一种低粘度液硫工质及其制备方法与应用 |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4335578A (en) * | 1980-05-30 | 1982-06-22 | Ford Aerospace & Communications Corporation | Solar power converter with pool boiling receiver and integral heat exchanger |
| US20060254576A1 (en) * | 2004-01-26 | 2006-11-16 | Jeno Marton | Method for gaining heat energy from a solar collector and heat energy absorbent substances usable in this method |
| DE102008046071A1 (de) * | 2008-09-05 | 2010-03-11 | Sterzel, Christoph Henrik | Die Anwendung von modifiziertem Schwefel als Wärmeträgerflüssigkeit |
| WO2010025692A1 (de) * | 2008-09-05 | 2010-03-11 | Sterzel, Hans-Josef | Die anwendung von modifiziertem, niedrigviskosem schwefel als wärmeträger- und wärmespeicherflüssigkeit |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3218802A (en) * | 1960-11-28 | 1965-11-23 | Aerojet General Co | Binary vapor power plant |
| US3440064A (en) * | 1966-04-04 | 1969-04-22 | Research Corp | Fire-retardant sulphur compositions |
| US3447941A (en) * | 1967-01-31 | 1969-06-03 | Stauffer Chemical Co | Sprayable sulfur road marking compositions |
| US3438680A (en) * | 1967-10-05 | 1969-04-15 | Shell Oil Co | Transportation of sulfur in pipelines as a sulfur-aqueous polysulfide slurry |
| US3606483A (en) * | 1969-04-28 | 1971-09-20 | Shell Oil Co | Slurrying of sulfur in liquid carrier |
| US3887330A (en) * | 1970-05-13 | 1975-06-03 | Shell Oil Co | Sulfur-hydrocarbon slurry pipeline transportation containing an inorganic corrosion inhibitor |
| US3676166A (en) * | 1970-09-28 | 1972-07-11 | Phillips Petroleum Co | Plasticized sulfur compositions |
| US4210458A (en) * | 1976-03-24 | 1980-07-01 | Chevron Research Company | Plasticized sulfur with improved thixotropy |
| CS185442B1 (en) * | 1976-06-08 | 1978-09-15 | Frantisek Polasek | Waste heat recuperation exchanger operable at work temperature of up to 1000 degrees celsius |
| US4326875A (en) * | 1978-12-26 | 1982-04-27 | Union Oil Company Of California | Sulfur product and method |
-
2010
- 2010-04-20 DE DE102010015632A patent/DE102010015632A1/de not_active Withdrawn
-
2011
- 2011-04-18 EP EP11717526A patent/EP2536807A1/de not_active Withdrawn
- 2011-04-18 WO PCT/EP2011/056111 patent/WO2011131610A1/de not_active Ceased
- 2011-04-18 BR BR112012027049A patent/BR112012027049A2/pt not_active IP Right Cessation
- 2011-04-18 US US13/641,951 patent/US20130037741A1/en not_active Abandoned
- 2011-04-18 CN CN201180019725XA patent/CN102834482A/zh active Pending
- 2011-04-18 AU AU2011244423A patent/AU2011244423A1/en not_active Abandoned
-
2012
- 2012-10-16 IL IL222471A patent/IL222471A0/en unknown
- 2012-10-19 CL CL2012002939A patent/CL2012002939A1/es unknown
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4335578A (en) * | 1980-05-30 | 1982-06-22 | Ford Aerospace & Communications Corporation | Solar power converter with pool boiling receiver and integral heat exchanger |
| US20060254576A1 (en) * | 2004-01-26 | 2006-11-16 | Jeno Marton | Method for gaining heat energy from a solar collector and heat energy absorbent substances usable in this method |
| DE102008046071A1 (de) * | 2008-09-05 | 2010-03-11 | Sterzel, Christoph Henrik | Die Anwendung von modifiziertem Schwefel als Wärmeträgerflüssigkeit |
| WO2010025692A1 (de) * | 2008-09-05 | 2010-03-11 | Sterzel, Hans-Josef | Die anwendung von modifiziertem, niedrigviskosem schwefel als wärmeträger- und wärmespeicherflüssigkeit |
Non-Patent Citations (1)
| Title |
|---|
| VON R.R. BACON: "The Viscosity of Sulfur", JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, vol. 65, 1943, pages 639 - 647 |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013178930A1 (fr) | 2012-06-01 | 2013-12-05 | Arkema France | Soufre liquide de faible viscosité |
| FR2991313A1 (fr) * | 2012-06-01 | 2013-12-06 | Arkema France | Soufre liquide de faible viscosite |
| CN104428241A (zh) * | 2012-06-01 | 2015-03-18 | 阿克马法国公司 | 低粘度液体硫 |
| US9334165B2 (en) | 2012-06-01 | 2016-05-10 | Arkema France | Low-viscosity liquid sulfur |
| CN104428241B (zh) * | 2012-06-01 | 2017-05-17 | 阿克马法国公司 | 低粘度液体硫 |
Also Published As
| Publication number | Publication date |
|---|---|
| CL2012002939A1 (es) | 2012-11-30 |
| IL222471A0 (en) | 2012-12-31 |
| AU2011244423A1 (en) | 2012-12-13 |
| EP2536807A1 (de) | 2012-12-26 |
| US20130037741A1 (en) | 2013-02-14 |
| CN102834482A (zh) | 2012-12-19 |
| DE102010015632A1 (de) | 2011-10-20 |
| BR112012027049A2 (pt) | 2016-07-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| WO2011131610A1 (de) | Wärmeträger-medium auf schwefel-basis und verwendung des wärmeträger-mediums | |
| EP0402304B1 (de) | Latentwärmespeichermittel und deren Verwendung | |
| EP2661556A2 (de) | Solarthermische kraftwerksanlage und verfahren zum betreiben einer solarthermischen kraftwerksanlage | |
| Cai et al. | Multi-energy driven form-stable phase change materials based on SEBS and reduced graphene oxide aerogel | |
| WO2013152748A1 (de) | Speicherkraftwerk | |
| DE102013219681A1 (de) | Verfahren und System zur Speicherung von elektrischer Energie | |
| WO2012142996A2 (de) | Wasseraufbereitung für wasserelektrolyse | |
| WO2012093012A1 (de) | Wärmeübertragungsmedium für solarthermische anlagen | |
| DE102012206541A1 (de) | Verfahren und Anordnung für die Hochtemperaturelektrolyse | |
| DE102010041460A1 (de) | Wärmetransfermedium, Verwendung dazu und Verfahren zum Betreiben einer solarthermischen Kraftwerksanlage | |
| EP2436040A2 (de) | Vorrichtung und verfahren zum kühlen von solarzellen mittels eines strömenden kühlmediums | |
| DE102016217090A1 (de) | Verfahren und System zum Speichern und Rückgewinnen von Wärmeenergie in einer Energieerzeugungsanlage | |
| EP2521692A1 (de) | Mischungen von alkalipolysulfiden | |
| DE102012007136A1 (de) | Rekonstruktion von Methan aus seinen Rauchgasen / Ein chemisches Speicherkraftwerk | |
| EP2556129B1 (de) | Fluider schwefel mit verbesserter viskosität als wärmeträger | |
| EP2350224A1 (de) | Die anwendung von modifiziertem, niedrigviskosem schwefel als wärmeträger- und wärmespeicherflüssigkeit | |
| Diekmann et al. | Energie | |
| EP3448952A1 (de) | Verwendung einer nitratsalzzusammensetzung als wärmeträger- oder wärmespeichermedium zur ersten inbetriebnahme einer diese medien enthaltenden vorrichtung | |
| JP2015030778A (ja) | 熱媒体組成物 | |
| DE102017114597A1 (de) | Verfahren und Vorrichtung zur solaren Erzeugung von Trinkwasser aus einer Wasser- Feststoff-Lösung | |
| DE102008046071A1 (de) | Die Anwendung von modifiziertem Schwefel als Wärmeträgerflüssigkeit | |
| DE102007016738A1 (de) | Neuer Wärmeträger für Solaranlagen | |
| DE102012020480A1 (de) | Verfahren zum Betreiben eines solarthermischen Kraftwerks sowie solarthermisches Kraftwerk | |
| EP3475566A1 (de) | Verfahren zur gasabtrennung aus hochtemperatur-wärmeträgerfluiden in solarwärmekraftwerken | |
| EP2904064B1 (de) | Verfahren zur speicherung von energie in salzschmelzen |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| WWE | Wipo information: entry into national phase |
Ref document number: 201180019725.X Country of ref document: CN |
|
| 121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 11717526 Country of ref document: EP Kind code of ref document: A1 |
|
| WWE | Wipo information: entry into national phase |
Ref document number: 2011717526 Country of ref document: EP |
|
| WWE | Wipo information: entry into national phase |
Ref document number: 8717/DELNP/2012 Country of ref document: IN |
|
| WWE | Wipo information: entry into national phase |
Ref document number: 13641951 Country of ref document: US |
|
| WWE | Wipo information: entry into national phase |
Ref document number: 2012002939 Country of ref document: CL |
|
| NENP | Non-entry into the national phase |
Ref country code: DE |
|
| ENP | Entry into the national phase |
Ref document number: 2011244423 Country of ref document: AU Date of ref document: 20110418 Kind code of ref document: A |
|
| REG | Reference to national code |
Ref country code: BR Ref legal event code: B01A Ref document number: 112012027049 Country of ref document: BR |
|
| ENP | Entry into the national phase |
Ref document number: 112012027049 Country of ref document: BR Kind code of ref document: A2 Effective date: 20121022 |